US5964916A - Mold for forming glass and method for forming glass - Google Patents

Mold for forming glass and method for forming glass Download PDF

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Publication number
US5964916A
US5964916A US09/069,988 US6998898A US5964916A US 5964916 A US5964916 A US 5964916A US 6998898 A US6998898 A US 6998898A US 5964916 A US5964916 A US 5964916A
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US
United States
Prior art keywords
mold
coating film
sidewall portion
plunger
thickness
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US09/069,988
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English (en)
Inventor
Yutaka Segawa
Toshihiro Ohashi
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AGC Inc
Original Assignee
Asahi Glass Co Ltd
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Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Assigned to ASAHI GLASS COMPANY LTD. reassignment ASAHI GLASS COMPANY LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: OHASHI, TOSHIHIRO, SEGAWA, YUTAKA
Application granted granted Critical
Publication of US5964916A publication Critical patent/US5964916A/en
Assigned to ASAHI GLASS COMPANY LTD. reassignment ASAHI GLASS COMPANY LTD. CHANGE OF CORPORATE ADDRESS Assignors: ASAHI GLASS COMPANY LTD.
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B11/00—Pressing molten glass or performed glass reheated to equivalent low viscosity without blowing
    • C03B11/06—Construction of plunger or mould
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B11/00—Pressing molten glass or performed glass reheated to equivalent low viscosity without blowing
    • C03B11/06—Construction of plunger or mould
    • C03B11/10—Construction of plunger or mould for making hollow or semi-hollow articles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B40/00—Preventing adhesion between glass and glass or between glass and the means used to shape it, hold it or support it
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B9/00—Blowing glass; Production of hollow glass articles
    • C03B9/30—Details of blowing glass; Use of materials for the moulds
    • C03B9/48—Use of materials for the moulds

Definitions

  • the present invention relates to a mold for forming glass, particularly to a mold for forming glass, which is useful for press-molding a glass product such as a panel or funnel for a cathode ray tube (CRT) for TV.
  • a glass product such as a panel or funnel for a cathode ray tube (CRT) for TV.
  • CRT cathode ray tube
  • a CRT for TV is produced in such a manner that a front panel, a funnel and a neck are prepared separately, and after applying phosphors to the inner surface of the panel and attaching a shallow mask and electrodes, they are bonded to form a CRT. Therefore, very strict quality control is required for the properties such as the surface irregularities, the surface roughness of the inner surface of the panel.
  • FIG. 1 shows a cross sectional schematic view illustrating the molding of a panel glass for a CRT. Molding of the panel is carried out by pressing a molten glass at a high temperature of about 1,000° C. by a mold. Therefore, the mold for forming glass is required to have mechanical strength and heat resistance and further required to have a property such as chemical stability against a high temperature glass.
  • a mold for forming glass which is suitable for such a purpose, one having chromium plating or nickel tungsten alloy plating applied on stainless steel, has been commonly used.
  • the plated coating film undergoes deterioration by use, and the mold body is reused by removing the coating film and applying plating afresh.
  • a plating bath such as a sergent bath, a mixed catalyst bath or a high efficiency bath, is used, and each contains highly toxic hexavalent chromium.
  • burr-like brittle marks (FIG. 2) are likely to form on the sidewall portion 14 of the plunger due to friction with the inside wall of the panel.
  • glass enters into such brittle marks formed on the sidewall portion of the plunger 11, and when the plunger 11 ascends, the brittle marks will abrade the entered glass to bring about scuff defects on the inside surface of the panel 10, and checks are likely to start from such defects, thus leading to deterioration of the quality of the panel.
  • a plated coating film of chromium has a drawback such that it is extremely weak against halogen-type impurities.
  • a plated coating film of nickel or cobalt, or an alloy containing such an element as the main component is excellent in a releasing property and free from formation of brittle marks which is likely to take place with chromium plating, and it tends to have ductile marks in to which glass hardly enters.
  • it has a feature that marks which bring about kinky threads on the inner surface of the panel, hardly form.
  • nickel-tungsten alloy plating can be used for film forming under such conditions that there will be no problem of toxicity or odor of reagents, whereby no scuff tends to form on the glass surface, and the frequency of using a releasing agent can be reduced. Accordingly, its use has recently been increased.
  • a plated coating film of nickel or cobalt, or an alloy containing such an element as the main component is likely to undergo, under a high temperature condition, mutual diffusion with iron in the stainless steel as the matrix material of the plunger and is readily oxidized, so that a chemically and mechanically stable oxide film tends to be hardly formed at the coating film surface. Accordingly, the surface roughness and the surface condition of the inner surface of the face panel presenting an image, which are most important from the viewpoint of the panel quality, tend to deteriorate, and it will be required to change the plunger after from 10,000 to 15,000 times of pressing operation, to remove the plated coating film and to carry out plating afresh.
  • Such a coating film has had a drawback that the useful life of the coating film is very short as compared with the above mentioned plated coating film of chromium which is likely to bring about formation of scuff defects on the inner surface of the panel.
  • the present inventors have conducted extensive studies to prevent formation of scuff on the inside surface of the panel caused by the brittle marks formed on the sidewall portion of the plunger and to overcome the chemical and mechanical deterioration of the coating film surface which occurs at the face portion of the plunger, so as to prevent deterioration of the surface roughness or surface condition of the inner surface of the face panel and thereby to obtain a panel having good quality free from defects on the inside-wall surface of the panel or the inner surface of the face of the panel.
  • the defects formed on the inside-wall surface of the panel and the inner surface of the face can be substantially reduced by selecting the outermost coating film to be formed on the plunger made of stainless steel, so that it will be a combination of coating films having characteristics suitable for the respective portions of the mold surface of the plunger, i.e. the coating film to be formed on the sidewall portion of the plunger is made of a ductile material and the coating film at the face portion is made of a high hardness material having oxidation resistance. Further, they have found that this can be applicable widely to molds for forming glass. The present invention has been accomplished on the basis of such discoveries.
  • the present invention provides a mold for forming glass, which comprises a mold body made of stainless steel and having a mold surface comprising a sidewall portion and a face portion continuous from the sidewall portion, a coating film of ductile material formed on the sidewall portion, and a coating film of high hardness material having oxidation resistance, formed on the face portion.
  • the present invention provides the above mold for forming glass, wherein the ductile material is nickel or cobalt, or an alloy containing nickel or cobalt as the main component.
  • the present invention provides the above mold for forming glass, wherein the high hardness material is at least one member selected from chromium oxide, aluminum oxide and zirconium oxide.
  • FIG. 1 is a cross sectional schematic view illustrating the molding of a panel glass for a CRT.
  • FIG. 2 is an enlarged view of portion A in FIG. 1.
  • FIG. 3 is a side view of a plunger as an embodiment of the present invention.
  • the mold of the present invention has a mold surface comprising a sidewall portion and a face portion continuous from the sidewall portion, on a mold body made of stainless steel.
  • the sidewall portion indicates the portion at which the mold and the glass abrade or are likely to abrade each other during the press molding of the glass.
  • a plunger for forming a panel of a CRT for TV it corresponds to the mold surface for forming the sidewall of the panel or the inner surface of the flange portion
  • the face portion means a portion other than the sidewall portion and corresponds to the mold surface for forming the image region of the panel or the inner surface of the face.
  • the present invention is applicable irrespective of a top or bottom mold or a male or female mold, so long as the mold has such a sidewall portion and a face portion, and due effects can be expected. However, its effects are particularly large with a plunger, as the abrasion between the glass and the mold is relatively vigorous during the molding.
  • the coating film or plated film to be formed on the mold surface intended by she present invention is the outermost coating film which will be in direct contact with the glass. However, if such the outermost coating film has a multi-layer structure, the coating film is meant for the entire multi-layer film.
  • the ductile material for the coating film to be formed on the sidewall portion of the mold is preferably such that the hardness is relatively small, and even when scuff is formed by abrasion with the glass, they will be ductile marks into which the glass will not enter, and burr-like brittle marks into which the glass enters, will be scarcely formed.
  • a single substance of nickel or cobalt, or an alloy thereof is effective.
  • an alloy having a nickel or cobalt content of at least 40 wt % is preferred.
  • a Group 6 element such as chromium, tungsten or molybdenum is suitable to obtain effects of suppressing high temperature oxidation, suppressing growth of crystal grains and maintaining high temperature strength during the molding of glass.
  • addition of phosphorus and/or boron is preferred to suppress the growth of crystal grains of the coating film during the molding of glass and to make crystallites fine or to convert them amorphous to form a structure where crystal grain boundaries are undeveloped.
  • the high hardness material for the coating film to be formed on the base portion of the mold is suitably one having oxidation resistance and a hardness higher than the above ductile material. Its hardness usually exceeds 800 kg/mm 2 as measured by a Vickers hardness meter. Particularly preferred is a material having a hardness of 900 kg/mm 2 or more. Specifically, it is preferred to make the coating film mainly from at least one member selected from chromium oxide, aluminum oxide and zirconium oxide. Even when the coating film is formed as a metal coating film of chromium, aluminum or zirconium, at least its surface layer will be oxidized to an oxide during its use. Accordingly, in the present invention, the material is represented by such an oxide. For the same reason, the coating film may be a coating film of chromium. Further, two or more high hardness materials may be used in combination. Such a combination may be in the form of a multi-layer film or a mixed coating film.
  • the coating films are to be formed by using these materials, in order to adequately secure the properties of the face portion of the mold, it is preferred to form an interlayer of chromium plating on the mold body made of stainless steel.
  • the coating film is formed on this interlayer, whereby peeling of the outermost coating film on the face portion of the mold can be facilitated by electrolytic peeling by utilizing this plated interlayer of chromium.
  • the coating film of ductile material and the interlayer of chromium plating may be prepared by a plating method, a CVD method, a PVD method or a hot spraying method of nickel, chromium or cobalt. Particularly preferred is a plating method in view of the film-forming speed, smoothness and costs.
  • chromium oxide, aluminum oxide or zirconium oxide can readily be prepared by a CVD method or a PVD method.
  • chromium oxide chromium as an interlayer may be subjected to suitable air oxidation treatment to form chromium oxide.
  • the thickness of the coating film of chromium oxide, aluminum oxide or zirconium oxide as a hardness material having oxidation resistance is preferably from 0.5 to 15 ⁇ m. If it is thinner than 0.5 ⁇ m, the quality of the glass surface property which can be brought about by forming such a hard film, can hardly adequately be secured. On the other hand, if it exceeds 15 ⁇ m, a stress appears to the coating film itself, and cracking or peeling is likely to take place when such a coating film has been formed.
  • the thickness of the entire film from the surface of the mold body to the ductile material coating film at the sidewall portion or to the high hardness material coating film at the face portion is preferably from 1 to 50 ⁇ m. If the thickness is thinner than 1 ⁇ m, it tends to be practically difficult to effectively cover the entire surface, and if it is thicker than 50 ⁇ m, the residual strain increases, and cracking or the like is likely to take place in the coating film.
  • the stainless steel constituting the mold body is preferably martensitic stainless steel in view of the mechanical strength, corrosion resistance, thermal conductivity, thermal expansion properties, etc.
  • a glass product of high quality can be press-molded by using the above mold.
  • the mold of the present invention is particularly suitable for forming a glass panel for a CRT.
  • the glass composition is not particularly limited.
  • a glass containing silicon oxide, sodium oxide, potassium oxide, strontium oxide and barium oxide is usually employed.
  • Example 1 to 12 a plunger 11 made of martensitic stainless steel SUS420J2 (JIS-G4303) was used as the mold body, as shown in FIG. 3, and prescribed coating films were formed on the sidewall portion 14 and on the face portion 15 of this plunger, respectively.
  • SUS420J2 martensitic stainless steel
  • the present invention is not limited to such a specific structure.
  • a CRT panel was formed. The results are shown in Table 1.
  • chromium was formed in a thickness of 15 ⁇ m by electroplating and then, chromium oxide was vapor-deposited in a thickness of 2 ⁇ m by a PVD method.
  • a CRT panel was formed. The results are shown in Table 1.
  • a CRT panel was formed. The results are shown in Table 1.
  • nickel was formed in a thickness of 40 ⁇ m by electroplating, and on the face portion, chromium was formed in a thickness 20 ⁇ m by electroplating, and then, chromium oxide was vapor-deposited in a thickness of 2 ⁇ m by a PVD method, and further aluminum oxide and zirconium oxide were vapor-deposited in a thickness of 1.5 ⁇ m and 2 ⁇ m, respectively.
  • a CRT panel was formed. The results are shown in Table 1.
  • chromium was formed in a thickness of 15 ⁇ m by electroplating and then, chromium oxide was vapor-deposited in a thickness of 2 ⁇ m by a PVD method.
  • a CRT panel was formed. The results are shown in Table 1.
  • chromium was formed in a thickness of 15 ⁇ m by electroplating
  • zirconium oxide was vapor-deposited in a thickness of 2 ⁇ m by a PVD method.
  • a CRT panel was formed. The results are shown in Table 1.
  • a CRT panel was formed. The results are shown in Table 1.
  • the mold of the present invention has coating films suitable for the particular portions or positions of the mold surface, selectively combined, whereby the moldability which gives a substantial influence over the quality of the molded products, or the life of the mold, is improved. If this mold is used for forming e.g. a CRT panel, it is possible to use the mold continuously for a long period of time even when the frequency of applying a releasing agent is reduced.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
US09/069,988 1997-05-27 1998-04-30 Mold for forming glass and method for forming glass Expired - Fee Related US5964916A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP9-137173 1997-05-27
JP9137173A JPH10330123A (ja) 1997-05-27 1997-05-27 ガラス成形用金型及びガラス成形方法

Publications (1)

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US5964916A true US5964916A (en) 1999-10-12

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US (1) US5964916A (zh)
JP (1) JPH10330123A (zh)
KR (1) KR100440995B1 (zh)
CN (1) CN1184154C (zh)
DE (1) DE19823710A1 (zh)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020167261A1 (en) * 2001-04-19 2002-11-14 Koninklijke Philips Electronics N.V. Method for manufacturing a glass panel for a cathode ray tube
US20020180336A1 (en) * 2001-06-01 2002-12-05 Koninklijke Philips Electronics N.V. Method for manufacturing a glass panel for a cathode ray tube
US20030005725A1 (en) * 2001-05-28 2003-01-09 Asahi Glass Company, Limited Glass forming mold and process for its production, and method for producing a glass product for a cathode ray tube
EP1285974A1 (en) * 2001-08-21 2003-02-26 Alphatek Hyperformance Coatings Ltd Coating compositions
US20060130522A1 (en) * 2004-12-21 2006-06-22 Konica Minolta Opto, Inc. Mold for molding optical glass and method of manufacturing optical glass element
US20090280208A1 (en) * 2008-05-08 2009-11-12 Honda Motor Co., Ltd. Mold and method for manufacturing mold
US20120128936A1 (en) * 2010-11-19 2012-05-24 Ryosuke Imajima Glass optical element and method for manufacturing the same
US20140206523A1 (en) * 2013-01-21 2014-07-24 Corning Incorporated High purity nickel molds for optical quality glass forming
US20150225275A1 (en) * 2012-09-25 2015-08-13 Konica Minolta, Inc. Glass component fabrication method

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19941571C1 (de) * 1999-09-01 2001-02-15 Schott Glas Bildschirm und Vorrichtungen zu seiner Herstellung
DE19941572C1 (de) * 1999-09-01 2001-01-18 Schott Glas Bildschirm und Vorrichtungen zu seiner Herstellung
AU7921100A (en) * 1999-10-22 2001-04-30 Castolin Eutectic International S.A. A coated mould and process for producing the mould
JP4698178B2 (ja) * 2004-07-13 2011-06-08 スピードファム株式会社 被研磨物保持用キャリア
CN1721346B (zh) * 2004-07-16 2011-03-23 鸿富锦精密工业（深圳）有限公司 模造玻璃的模仁制造方法
JP5569927B2 (ja) * 2008-02-08 2014-08-13 学校法人東京理科大学 金属膜を有する構造体の製造方法及びそれにより製造される構造体
JP5077251B2 (ja) * 2009-01-20 2012-11-21 コニカミノルタアドバンストレイヤー株式会社 金型、金型の製造方法、ガラスゴブの製造方法及びガラス成形体の製造方法
CN104313527B (zh) * 2014-10-22 2017-02-08 福耀集团（上海）汽车玻璃有限公司 一种提高汽车玻璃凹模耐磨性能的方法
WO2019060739A1 (en) * 2017-09-21 2019-03-28 Entegris, Inc. COATINGS FOR GLASS-FORMING MOLDS AND MOLDS COMPRISING THE SAME
KR102462946B1 (ko) * 2022-07-01 2022-11-04 강한일 유리 제품 제조용 금형 제조방법

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US3589986A (en) * 1969-04-28 1971-06-29 Owens Illinois Inc Method of fabricating a glass forming apparatus
US3792986A (en) * 1972-05-08 1974-02-19 Scott Browne Corp Method of fabricating, using and reconditioning apparatus for forming optical quality articles from molten glass and forming elements for use therein
US4218243A (en) * 1972-09-20 1980-08-19 Hitachi Metals, Ltd. Fully martensitic steel for a metal mold for molding glass and the metal mold
US4251254A (en) * 1978-05-18 1981-02-17 U.S. Philips Corporation Tools for the handling and shaping of glass
US4382811A (en) * 1980-03-27 1983-05-10 Castolin S.A. Method of producing protective coatings on metal parts to be used in contact with molten glass
US5120341A (en) * 1990-02-20 1992-06-09 Ishizuka Garasu Kabushiki Kaisha Method for manufacturing a glass container having a large impact strength using permanent and non permanent coatings on the apparatus

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Publication number Priority date Publication date Assignee Title
JP3653749B2 (ja) * 1994-08-15 2005-06-02 旭硝子株式会社 ブラウン管ガラス成型用金型及びブラウン管用ガラス製品の成型方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3589986A (en) * 1969-04-28 1971-06-29 Owens Illinois Inc Method of fabricating a glass forming apparatus
US3792986A (en) * 1972-05-08 1974-02-19 Scott Browne Corp Method of fabricating, using and reconditioning apparatus for forming optical quality articles from molten glass and forming elements for use therein
US4218243A (en) * 1972-09-20 1980-08-19 Hitachi Metals, Ltd. Fully martensitic steel for a metal mold for molding glass and the metal mold
US4251254A (en) * 1978-05-18 1981-02-17 U.S. Philips Corporation Tools for the handling and shaping of glass
US4382811A (en) * 1980-03-27 1983-05-10 Castolin S.A. Method of producing protective coatings on metal parts to be used in contact with molten glass
US5120341A (en) * 1990-02-20 1992-06-09 Ishizuka Garasu Kabushiki Kaisha Method for manufacturing a glass container having a large impact strength using permanent and non permanent coatings on the apparatus

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6807825B2 (en) * 2001-04-19 2004-10-26 Koninklijke Philips Electronics N.V. Method for manufacturing a glass panel for a cathode ray tube
US20020167261A1 (en) * 2001-04-19 2002-11-14 Koninklijke Philips Electronics N.V. Method for manufacturing a glass panel for a cathode ray tube
CN1310271C (zh) * 2001-05-28 2007-04-11 旭硝子株式会社 玻璃成形用模具及其生产方法,和阴极射线管用的玻璃产品的生产方法
US20030005725A1 (en) * 2001-05-28 2003-01-09 Asahi Glass Company, Limited Glass forming mold and process for its production, and method for producing a glass product for a cathode ray tube
US6868699B2 (en) * 2001-05-28 2005-03-22 Asahi Glass Company, Limited Glass forming mold
US20020180336A1 (en) * 2001-06-01 2002-12-05 Koninklijke Philips Electronics N.V. Method for manufacturing a glass panel for a cathode ray tube
US6884137B2 (en) * 2001-06-01 2005-04-26 Koninklijke Philips Electronics N.V. Method for manufacturing glass panel for a cathode ray tube
EP1285974A1 (en) * 2001-08-21 2003-02-26 Alphatek Hyperformance Coatings Ltd Coating compositions
US20100064727A1 (en) * 2004-12-21 2010-03-18 Konica Minolta Opto, Inc. Method of Manufacturing An Optical Glass Element
US20060130522A1 (en) * 2004-12-21 2006-06-22 Konica Minolta Opto, Inc. Mold for molding optical glass and method of manufacturing optical glass element
US8327663B2 (en) 2004-12-21 2012-12-11 Konica Minolta Opto, Inc. Method of manufacturing an optical glass element
US20090280208A1 (en) * 2008-05-08 2009-11-12 Honda Motor Co., Ltd. Mold and method for manufacturing mold
US20120128936A1 (en) * 2010-11-19 2012-05-24 Ryosuke Imajima Glass optical element and method for manufacturing the same
CN102557394A (zh) * 2010-11-19 2012-07-11 柯尼卡美能达精密光学株式会社 玻璃光学元件及其制造方法
CN102557394B (zh) * 2010-11-19 2014-07-30 柯尼卡美能达精密光学株式会社 玻璃光学元件及其制造方法
US20150225275A1 (en) * 2012-09-25 2015-08-13 Konica Minolta, Inc. Glass component fabrication method
US20140206523A1 (en) * 2013-01-21 2014-07-24 Corning Incorporated High purity nickel molds for optical quality glass forming
US9266768B2 (en) * 2013-01-21 2016-02-23 Corning Incorporated High purity nickel molds for optical quality glass forming
US9475723B2 (en) 2013-01-21 2016-10-25 Corning Incorporated Molds for shaping glass and methods for making the same
TWI619683B (zh) * 2013-01-21 2018-04-01 康寧公司 用於光學品質玻璃之形成上的高純度鎳模具

Also Published As

Publication number Publication date
CN1200358A (zh) 1998-12-02
DE19823710A1 (de) 1998-12-03
KR100440995B1 (ko) 2004-10-14
CN1184154C (zh) 2005-01-12
KR19980087339A (ko) 1998-12-05
JPH10330123A (ja) 1998-12-15

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